WO2011096235A1 - 更生タイヤ - Google Patents
更生タイヤ Download PDFInfo
- Publication number
- WO2011096235A1 WO2011096235A1 PCT/JP2011/000650 JP2011000650W WO2011096235A1 WO 2011096235 A1 WO2011096235 A1 WO 2011096235A1 JP 2011000650 W JP2011000650 W JP 2011000650W WO 2011096235 A1 WO2011096235 A1 WO 2011096235A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- rubber
- tire
- mass
- layer
- retread
- Prior art date
Links
- 0 *N(*)C(SSC(N(*)*)=S)=S Chemical compound *N(*)C(SSC(N(*)*)=S)=S 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C11/00—Tyre tread bands; Tread patterns; Anti-skid inserts
- B60C11/02—Replaceable treads
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0016—Compositions of the tread
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C11/00—Tyre tread bands; Tread patterns; Anti-skid inserts
- B60C11/0041—Tyre tread bands; Tread patterns; Anti-skid inserts comprising different tread rubber layers
- B60C11/005—Tyre tread bands; Tread patterns; Anti-skid inserts comprising different tread rubber layers with cap and base layers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3415—Five-membered rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/39—Thiocarbamic acids; Derivatives thereof, e.g. dithiocarbamates
- C08K5/40—Thiurams, i.e. compounds containing groups
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D30/00—Producing pneumatic or solid tyres or parts thereof
- B29D30/06—Pneumatic tyres or parts thereof (e.g. produced by casting, moulding, compression moulding, injection moulding, centrifugal casting)
- B29D30/52—Unvulcanised treads, e.g. on used tyres; Retreading
- B29D30/54—Retreading
- B29D2030/544—Applying an intermediate adhesive layer, e.g. cement or cushioning element between carcass and tread
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C11/00—Tyre tread bands; Tread patterns; Anti-skid inserts
- B60C11/0008—Tyre tread bands; Tread patterns; Anti-skid inserts characterised by the tread rubber
- B60C2011/0016—Physical properties or dimensions
- B60C2011/0025—Modulus or tan delta
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31826—Of natural rubber
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31826—Of natural rubber
- Y10T428/3183—Next to second layer of natural rubber
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31909—Next to second addition polymer from unsaturated monomers
- Y10T428/31924—Including polyene monomers
Definitions
- the present invention relates to a retread tire using a cushion rubber for a retread tire made of a rubber composition having a specific elastic modulus (modulus), and more particularly to a retread tire suitable for manufacturing by a cold (COLD) system.
- module specific elastic modulus
- TBR retreaded tires for truck and bus radial tires
- base tires the tread surface of tires (hereinafter referred to as “base tires”) that have been worn out and have finished their primary life has been buffed.
- a method of attaching a vulcanized tread rubber portion (precure tread) that has been vulcanized in advance is known as one of typical methods. This method is called by a name such as a cold (COLD) method or a precure method, and is distinguished from a hot (HOT) method in which an unvulcanized tread rubber is placed on a base tire and mold vulcanized.
- COLD cold
- HET hot
- an unvulcanized cushion rubber is pasted on the base tire, and further, the precure tread is pasted thereon, and then the vulcanized can is used.
- a method of heating at a temperature of 110 to 140 ° C. is common.
- the cushion rubber used in this system flows into the buffs of the base tire, smoothes the adhesive surface, and co-vulcanizes with both the base tire and the pre-cured tread to ensure the adhesion between the pre-cured tread and the base tire. It has a function.
- the cushion rubber is located between the base tire and the precure tread, that is, in the part where stress is concentrated, and when using an actual retreaded tire, the adhesion and fracture resistance of this part is the durability of the retreaded tire. (Precure tread should not be peeled off from the base tire). Therefore, it is conventionally known that such a cushion rubber must have a fracture resistance (TB) equal to or greater than that of the surface tire rubber and precure tread rubber of the base tire.
- TB fracture resistance
- Patent Documents 1 to 3 disclose techniques for achieving both fracture resistance (TB) including after aging and vulcanization productivity, low viscosity, or high clay properties.
- Patent Document 4 describes that a high TB and a low elastic modulus are preferable for securing the peeling resistance during running.
- Patent Document 5 discloses a cushion rubber having a 100% modulus in a range of 80 to 120% as compared with a 100% modulus of a base tire carcass coating rubber. It has been shown that it is effective in improving separation failure.
- JP 2002-69245 A JP 2008-94266 A JP 2009-108117 A JP 2002-69237 A JP-A-8-216616
- the adhesive force between the vulcanized rubber and the unvulcanized rubber tends to be weaker than the co-cured adhesion between the unvulcanized rubbers. Since the retreading method for aircraft tires has conventionally been adopted, the location where vulcanized rubber and unvulcanized rubber are bonded is limited between the base tire and the cushion rubber. No investigation has been made on the adhesion between the precure tread rubber.
- Patent Document 5 although the rigidity step between the cushion rubber and the carcass coating rubber is defined, in actuality, it is necessary to provide the buff surface of the base tire at a certain distance from the carcass or the belt. Since the carcass coating rubber is not exposed on the surface of the buff surface in contact with the rubber, it has not yet been specified up to the rigidity step between the unvulcanized cushion rubber and the base tire surface in direct contact.
- an object of the present invention is to provide a retread tire using a cushion rubber for a retread tire that can further improve the prevention of separation failure while effectively suppressing the broad-out in the cushion rubber layer.
- the present inventors have found a cushion rubber for retread tires made of a rubber composition having a specific elastic modulus (modulus), and have completed the present invention.
- the retreaded tire of the present invention is In a retread tire comprising cushion rubber for retread tires, a base tire, and a precure tread rubber composed of one or more rubber layers,
- the retread cushion rubber contains natural rubber and / or synthetic polyisoprene rubber in an amount of 60 to 100% by mass in 100% by mass of the rubber component, and has a HAF grade or higher relative to 100 parts by mass of the rubber component.
- the rubber layer (A) comprising the cushion rubber for retread tire has a 100% modulus (A M ) of 3.0 MPa or more and less than 6.0 MPa, and the outermost layer (B) of the base tire and the precure tread rubber
- the innermost layer (C) is formed from a rubber composition containing natural rubber and / or synthetic isoprene rubber in an amount of 60 to 100% by mass in 100% by mass of the rubber component.
- the rubber composition forming the cushion rubber for retread tire is selected from the group consisting of a compound represented by the following formula (I) and a compound represented by the following formula (II) with respect to 100 parts by mass of the rubber component.
- the at least one thiuram compound may be contained in an amount of 0.1 to 4.0 parts by mass.
- R 1 to R 4 are each independently a benzyl group or an alkyl group having 1 to 18 carbon atoms, and x is an average number of 2 to 18);
- R 5 to R 8 are each independently a benzyl group or an alkyl group having 1 to 18 carbon atoms).
- the rubber composition for forming the cushion rubber for retread tires may further contain 1.0 to 3.0 parts by mass of a bismaleimide compound represented by the following (III) with respect to 100 parts by mass of the rubber component. May be included.
- a bismaleimide compound represented by the following (III) represents a divalent aromatic group having 6 to 18 carbon atoms or a divalent alkyl aromatic group having 7 to 24 carbon atoms, and y and z are each independently 0 to Represents an integer of 3.
- 100% modulus (A M ) of the rubber layer (A) made of the cushion rubber, 100% modulus (B M ) of the outermost layer (B) of the base tire, and the innermost layer (C of the precure tread rubber) ) Has a 100% modulus (C M ) of the following formulas (i) and (ii): (I) 60% ⁇ A M / B M ⁇ 140% (Ii) 60% ⁇ A M / C M ⁇ 140% It is desirable to satisfy this relationship.
- Such a retreaded tire is preferably applied to an aircraft retreaded tire that is vulcanized and bonded by a precure method.
- the adhesiveness at the interface between the base tire and the cushion rubber and the interface between the cushion rubber and the precure tread rubber is extremely excellent while effectively preventing the broad-out in the cushion rubber layer. This can effectively prevent separation from occurring. Therefore, extremely excellent durability can be exhibited as a retreaded tire employing the COLD method. Moreover, the obtained retreaded tire is particularly useful as an aircraft retreaded tire that is placed in a very severe use environment.
- the retread tire of the present invention is In a retread tire comprising cushion rubber for retread tires, a base tire, and a precure tread rubber composed of one or more rubber layers,
- the retread cushion rubber contains natural rubber and / or synthetic polyisoprene rubber in an amount of 60 to 100% by mass in 100% by mass of the rubber component, and has a HAF grade or higher relative to 100 parts by mass of the rubber component.
- the rubber layer (A) comprising the cushion rubber for retread tire has a 100% modulus (A M ) of 3.0 MPa or more and less than 6.0 MPa, and the outermost layer (B) of the base tire and the precure tread rubber
- the innermost layer (C) is formed of a rubber composition containing natural rubber and / or synthetic isoprene rubber in an amount of 60 to 100% by mass in 100% by mass of the rubber component.
- the outermost layer (B) of the base tire means a rubber layer in the vicinity of the surface of the base tire after buffing, that is, a rubber layer in a range from the top surface of the base tire to a depth of 1 mm in the tire center direction.
- the innermost layer (C) of the precured tread rubber is a layer in the vicinity of the interface with the rubber layer (A), that is, from the innermost surface of the precured tread rubber to the depth of 0.5 mm in the inner direction of the precured tread rubber layer. Means a rubber layer in the range.
- the retread tire of the present invention comprises a specific retread tire cushion rubber described later, a base tire, and a precure tread rubber composed of one or more rubber layers, and is an old tread remaining in a used tire.
- Precured tread rubber consisting of multiple pre-vulcanized rubber layers is pasted on the crown of the base tire from which the rubber has been removed by bubbling through a rubber layer (A) consisting of cushion rubber for unvulcanized retreaded tires.
- A rubber layer
- the cushion rubber for retread tires used in the present invention contains natural rubber and / or synthetic polyisoprene rubber in an amount of 60 to 100% by mass in 100% by mass of the rubber component, and HAF class with respect to 100 parts by mass of the rubber component. Formed from a rubber composition containing the above highly reinforcing carbon black in an amount of 30 to 50 parts by mass;
- the 100% modulus of the rubber layer made of cushion gum for retread tire (A) (A M) is less than or 3.0 MPa 5.0 MPa.
- the rubber composition used for the cushion rubber for retread tires contains natural rubber and / or synthetic polyisoprene rubber in an amount of 60 to 100% by mass, preferably 80 to 100% by mass in 100% by mass of the rubber component.
- the outermost layer (B) of the cushion rubber and the base tire corresponds to unvulcanized rubber and vulcanized rubber, respectively, and thus has an interface that is difficult to co-vulcanize.
- the amount of natural rubber and / or synthetic polyisoprene rubber in 100% by mass of the rubber component of the rubber composition forming the cushion rubber is less than 60% by mass, the rubber composition forming the outermost tire layer (B) is durable.
- Natural rubber and / or synthetic polyisoprene rubber is required in 60% by mass or more in 100% by mass of the rubber component in order to ensure the properties, so that the co-curability is insufficient and the adhesiveness at the interface is reduced, Separation is likely to occur.
- usable rubber components are not particularly limited, but styrene-butadiene rubber (SBR), polybutadiene (BR), acrylonitrile-butadiene rubber (NBR), silicone rubber, fluorine elastomer , Ethylene-acrylic rubber, ethylene-propylene rubber (EPR), ethylene-propylene-diene monomer (EPDM) rubber, butyl rubber, polychloroprene, hydrogenated nitrile rubber, styrene-butadiene rubber (SBR), polybutadiene (BR) ) Is preferred.
- SBR styrene-butadiene rubber
- BR polybutadiene
- NBR acrylonitrile-butadiene rubber
- silicone rubber fluorine elastomer
- Ethylene-acrylic rubber ethylene-propylene rubber (EPR), ethylene-propylene-diene monomer (EPDM) rubber
- EPDM ethylene-propylene-diene monomer
- SBR styrene-butadiene rubber
- high reinforcing carbon black of HAF grade or higher is used as carbon black.
- HAF grade or higher highly reinforcing carbon black is a carbon whose specific surface area (m 2 / g) evaluated by iodine adsorption amount, DBP adsorption amount, etc. is equal to or larger than that of HAF grade carbon black. Black is meant, for example, in addition to HAF (N330), ISAF (N220) and the like. If carbon black of less than HAF class (for example, FEF class, GPF class) is used, it may be difficult to combine high fracture strength and high heat resistance.
- HAF class for example, FEF class, GPF class
- examples of the high-reinforcing carbon black higher than the HAF class include N330, N335, N339, N343, N347, N351, N356, N358, N375, N220, and N234.
- N330, N335, N339, N343, N347, and N220 are more preferable.
- the rubber composition used for the cushion rubber for retread tires is 30 to 50 parts by mass, preferably 35 to 50 parts by mass, more preferably 35 to 50 parts by mass of the HAF grade or higher high-reinforcing carbon black with respect to 100 parts by mass of the rubber component. It is contained in an amount of 35 to 45 parts by mass. If the blending amount of the carbon black is less than 30 parts by mass, the mechanical strength is insufficient, and if it exceeds 50 parts by mass, the heat generation characteristics may be deteriorated, and the viscosity increase and adhesive strength when unvulcanized. May occur, and the followability to the uneven surface on the buff surface may be insufficient, or adhesion failure may occur when unvulcanized.
- the rubber composition used for the cushion rubber for retread tire further contains at least one thiuram compound selected from the group consisting of a compound represented by the following formula (I) and a compound represented by the following formula (II). Is preferred.
- the COLD method is adopted.
- the vulcanization speed is increased during vulcanization. While a faster speed is desirable, it is required not to scorch until the molding process of retreaded tires.
- by blending the thiuram compound it is easy to achieve both good vulcanization speed and scorch resistance.
- R 1 to R 4 are each independently a benzyl group or an alkyl group having 1 to 18 carbon atoms, preferably a benzyl group or an alkyl group having 4 to 12 carbon atoms.
- alkyl group having 1 to 18 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, Examples include a linear or branched group such as a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, and an octadecyl group.
- x is an average number of 2 to 18, preferably 6 to 12.
- Examples of the thiuram compound represented by the formula (I) include 1,6-bis (N, N′-dibenzylthiocarbamoyldithio) -hexane, 1,6-bis (N, N′-di (2-ethylhexyl). ) Thiocarbamoyldithio) -hexane.
- R 5 to R 8 are each independently a benzyl group or an alkyl group having 1 to 18 carbon atoms, preferably a benzyl group or an alkyl group having 4 to 12 carbon atoms, Examples of the 18 alkyl group include the same as those described above.
- Examples of the thiuram compounds represented by the above formula (II) include tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, tetrakis (2-ethylhexyl) thiuram disulfide and the like.
- thiuram compounds may be used alone or in combination of two or more.
- 1,6-bis (N, N′-diisobutylthiocarbamoyldithio) -hexane is preferable, and examples of such a commercial product include VULCUREN KA9188 (registered trademark, manufactured by LANXESS).
- the thiuram-based compound is preferably added in an amount of 0.1 to 4.0 parts by mass, and more preferably 0.2 to 1.0 parts by mass with respect to 100 parts by mass of the rubber component.
- the blending amount of the thiuram compound is less than 0.1 parts by mass, the desired vulcanization acceleration effect may not be sufficiently obtained, and when it exceeds 4.0 parts by mass, the scorch resistance and the heat aging resistance are deteriorated. May decrease more than necessary.
- the rubber composition used for the retread cushion rubber preferably further contains a bismaleimide compound represented by the following formula (III).
- a bismaleimide compound represented by the following formula (III) By blending such a compound, the elastic modulus and heat aging resistance can be improved. In general, it is very difficult to eliminate the rigidity difference between the cushion rubber and adjacent rubber, but even if there is a possibility that some distortion is concentrated due to insufficient rigidity of the rubber layer made of cushion rubber. Good heat resistance can be easily ensured.
- A represents a divalent aromatic group having 6 to 18 carbon atoms or a divalent alkyl aromatic group having 7 to 24 carbon atoms. Specific examples of such A include a group represented by the following formula.
- Y and z each independently represent an integer of 0 to 3.
- y or z is 4 or more, the molecular weight becomes too large, and there is a possibility that the desired heat resistance improvement effect may not be sufficiently obtained for the blending amount, which is not preferable.
- bismaleimide compound represented by the above formula (III) examples include N, N′-1,2-phenylenebismaleimide, N, N′-1,3-phenylenebismaleimide, N, N′-1 , 4-phenylene bismaleimide, N, N ′-(4,4′-diphenylmethane) bismaleimide, N, N ′-(4,4′-diphenyl ether) bismaleimide, 2,2-bis [4- (4- Maleimidophenoxy) phenyl] propane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane.
- These bismaleimide compounds may be used alone or in combination of two or more. Of these, N, N ′-(4,4′-diphenylmethane) bismaleimide is preferred.
- the bismaleimide compound is contained in an amount of preferably 1.0 to 3.0 parts by mass in total with respect to 100 parts by mass of the rubber component, and more preferably 1.0 to 2.0 parts by mass from the viewpoint of cost. Is good.
- the blending amount of the bismaleimide compound is less than 1.0 part by mass, the effect of improving the heat resistance tends not to be sufficiently exhibited, and when it exceeds 3.0 parts by mass, the fracture characteristics and the bending fatigue resistance are more than necessary. May be reduced.
- the rubber composition includes a vulcanizing agent, a vulcanization accelerator, an oil, a tackifier, an anti-aging agent, a fatty acid, a softening agent, a peptizer, a vulcanization retarder, a filler such as silica, an activity
- a vulcanization accelerator such as N-tert-butyl-2-benzothiazolylsulfenamide (BBS), 2-mercaptobenzothiazole, diphenylguanidine (DPG), and the like.
- BBS N-tert-butyl-2-benzothiazolylsulfenamide
- DPG diphenylguanidine
- Noxeller M, Noxeller D both are registered trademarks, manufactured by Ouchi Shinsei Chemical Co., Ltd.
- the 100% modulus of the rubber layer (A) comprising the cushion rubber for retread tires of the present invention is 3.0 MPa or more and less than 6.0 MPa, preferably 3.0 to 3.5 MPa, more preferably 4.0 to 5.0 MPa. It is.
- the 100% modulus is less than 3.0 MPa or 6.0 MPa or more, there is a high possibility that a rigidity step is generated at the interface between the adjacent rubber and the cushion rubber constituting the base tire or the precure tread. Tends to cause separation due to concentration of distortion.
- the pressure is less than 3.0 MPa, high-speed and high-load inputs tend to concentrate on the cushion rubber layer, and there is a possibility that broadout occurs in the layer.
- the rubber adjacent to the reclaimed tire cushion rubber is usually coated with cement rubber in which the rubber is dissolved in a solvent, and after the solvent is dried, a rubber layer of about several ⁇ m is formed. This rubber layer is unvulcanized.
- the rubber layer (A) made of the cushion rubber for retread tire includes the rubber layer made of such cement rubber.
- the rubber composition forming the outermost layer (B) of the above tire and the innermost layer (C) of the precure tread rubber is composed of 60 to 100% by mass of natural rubber and / or synthetic polyisoprene rubber in 100% by mass of the rubber component. In an amount of 80 to 100% by weight.
- Carcass coating rubber and belt coating rubber which are skeleton members of high-speed and high-load tires, are made of natural rubber and synthetic polyisoprene rubber, and the outermost layer (B) of the base tire is rigid with these skeleton members. Since the level difference comes in contact with a large interface, it is necessary to exhibit a high degree of co-vulcanization with these skeleton members. Accordingly, when 100% by mass of the rubber component in the outermost layer (B) of the base tire is less than 60% by mass of natural rubber and / or synthetic polyisoprene rubber, co-curability with the skeleton member is insufficient, and the interface May cause separation.
- the innermost layer (C) and the rubber layer (A) of the precure tread rubber correspond to vulcanized rubber and unvulcanized rubber, respectively, and thus have an interface that is difficult to co-vulcanize,
- 100% by mass of the rubber component in the innermost layer (C) of the precure tread rubber is less than 60% by mass of natural rubber and / or synthetic polyisoprene rubber, these co-vulcanizates are insufficient and adhesion at the interface. May deteriorate and separation may occur.
- the rubber component and compounding agent that can be used for the outermost layer (B) of the above-mentioned tire and the innermost layer (C) of the precure tread rubber are not particularly limited other than natural rubber and synthetic polyisoprene rubber.
- the same as (A) can be used.
- the precure tread rubber may be composed of one or more rubber layers. When the precure tread rubber is composed of a plurality of layers, the rubber is used as a layer other than the innermost layer (C) in the precure tread rubber.
- a desired reinforcing fabric layer made of a coated cord layer or the like may be provided.
- 100% modulus (A M ) of the rubber layer (A) made of the cushion rubber, 100% modulus (B M ) of the outermost layer (B) of the base tire, and the innermost layer (C of the precure tread rubber) ) Has a 100% modulus (C M ) of the following formulas (i) and (ii): (I) 60% ⁇ A M / B M ⁇ 140% (Ii) 60% ⁇ A M / C M ⁇ 140% It is desirable to satisfy this relationship, and it is more desirable to satisfy the relationship of the following formulas (i-1) and (ii-1). (I-1) 80% ⁇ A M / B M ⁇ 120% (Ii-1) 80% ⁇ AM / CM ⁇ 120%
- a M / BM and A M / C M are less than 60% or more than 120%, a rigidity step occurs at the interface between the rubber layer (A) and the rubber layer of the base tire or the precure tread rubber, resulting in distortion. It becomes easy to concentrate, causing a decrease in interfacial adhesion and causing separation. Further, if A M / BM and A M / CM are less than 60%, the distortion of the rubber layer (A) itself may increase, and the heat generation tends to be excessive, which causes broad-out destruction. It becomes easy.
- Aircraft tires are often placed in extremely harsh usage environments, and such retreaded tires are vulcanized and bonded in a precure manner and applied to aircraft retreaded tires. Performance and durability can be demonstrated.
- Examples 1 to 7 using the above cushion rubber, base tire rubber, and precure tread rubber are retreaded tires that exhibit superior durability compared to Comparative Examples 1 to 8. I understand.
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Tires In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
更生タイヤ用クッションゴムと、台タイヤと、1層以上のゴム層からなるプレキュアトレッドゴムとを具える更生タイヤにおいて、
前記更生タイヤ用クッションゴムが、ゴム成分100質量%中、天然ゴム及び/又は合成ポリイソプレンゴムを60~100質量%の量で含むとともに、前記ゴム成分100質量部に対し、HAF級以上の高補強性カーボンブラックを30~50質量部の量で含むゴム組成物から形成されてなり、
前記更生タイヤ用クッションゴムからなるゴム層(A)の100%モジュラス(AM)が、3.0MPa以上6.0MPa未満であり、かつ
前記台タイヤの最外層(B)及び前記プレキュアトレッドゴムの最内層(C)が、ゴム成分100質量%中、天然ゴム及び/又は合成イソプレンゴムを60~100質量%の量で含むゴム組成物から形成されてなることを特徴とする。
(式(I)中、R1~R4はそれぞれ独立してベンジル基又は炭素数1~18のアルキル基であり、xは平均数として2~18である。);
(式(II)中、R5~R8はそれぞれ独立してベンジル基又は炭素数1~18のアルキル基である。)。
(式(III)中、Aは、炭素数6~18の二価の芳香基、又は炭素数7~24の二価のアルキル芳香族基を示し、yおよびzは、それぞれ独立して0~3の整数を示す。)。
(i)60%≦AM/BM≦140%
(ii)60%≦AM/CM≦140%
の関係を満たすのが望ましい。
また、得られる更生タイヤは、非常に過酷な使用環境下におかれる航空機用更生タイヤとして、特に有用である。
本発明の更生タイヤは、
更生タイヤ用クッションゴムと、台タイヤと、1層以上のゴム層からなるプレキュアトレッドゴムとを具える更生タイヤにおいて、
前記更生タイヤ用クッションゴムが、ゴム成分100質量%中、天然ゴム及び/又は合成ポリイソプレンゴムを60~100質量%の量で含むとともに、前記ゴム成分100質量部に対し、HAF級以上の高補強性カーボンブラックを30~50質量部の量で含むゴム組成物から形成されてなり、
前記更生タイヤ用クッションゴムからなるゴム層(A)の100%モジュラス(AM)が、3.0MPa以上6.0MPa未満であり、かつ
前記台タイヤの最外層(B)及び前記プレキュアトレッドゴムの最内層(C)が、ゴム成分100質量%中、天然ゴム及び/又は合成イソプレンゴムを60~100質量%の量で含むゴム組成物から形成されてなることを特徴としている。
前記ゴム成分100質量部に対し、HAF級以上の高補強性カーボンブラックを30~50質量部の量で含むゴム組成物から形成されてなり、
前記更生タイヤ用クッションゴムからなるゴム層(A)の100%モジュラス(AM)が、3.0MPa以上5.0MPa未満である。
xは平均数として2~18であり、好ましくは6~12である。
なお、上記プレキュアトレッドゴムは1層以上のゴム層からなるものであればよく、複数層からなるものである場合には、プレキュアトレッドゴム内の最内層(C)以外の層として、ゴム被覆コード層等からなる所望の補強ファブリック層を設けてもよい。
(i)60%≦AM/BM≦140%
(ii)60%≦AM/CM≦140%
の関係を満たすのが望ましく、下記式(i-1)及び(ii-1)の関係を満たすのがより望ましい。
(i-1)80%≦AM/BM≦120%
(ii-1)80%≦AM/CM≦120%
[実施例1~7、比較例1~8]
表1~2に示す配合処方に従い、その他、ゴム成分100質量部に対して、ステアリン酸3.0質量部、亜鉛華5.0質量部、老化防止剤(ノクラック6C、大内新興化学工業社製)2.0質量部、硫黄1.5~3.5質量部、加硫促進剤をさらに適量添加し、各々のゴム組成物をクッションゴム層(A)、台タイヤの最外層(B)、及びプレキュアトレッドゴムの最内層(C)に適用した航空機用ラジアル更生タイヤ(サイズ:30×8.8 R15 16PR)をCOLD方式により作製した。得られた更生タイヤを用いて、以下の評価を行った。
得られた更生タイヤから各部材のゴムの厚さ0.3mmのシートを切り出し、DINS3Aタイプ刃型で切り抜いてテスト・サンプルを作成し、このサンプルを100mm/分の引っ張り速度の条件で、クッションゴム層(A)の100%モジュラス(AM)、台タイヤの最外層(B)の100%モジュラス(BM)、プレキュアトレッドゴムの最内層(C)の100%モジュラス(CM)を測定し、各々モジュラス対比AM/BM、AM/CMを求めた。結果を表1~2に示す。
得られた更生タイヤをリムに取り付けたリム組立体を、ドラム試験機に取り付け、アメリカ航空管理局(FAA:U.S. Federal Aviation Administration)の承認試験「TSO‐C62 d」を1サイクル実施し、下記基準により評価を行った。結果を表1~2に示す。
故障なし:ゴム層(A)内にブロードアウトが発生せず、またゴム層(A)~(C)のいずれの界面にも異常がなかった。
ブロードアウト:ゴム層(A)内にブロードアウトが発生した。
セパレーション:ゴム層(A)~(C)のいずれかの界面近傍でセパレーション故障が発生した。
※2: 四塩化スズ変性スチレン-ブタジエンゴム、JSR社製(スチレン含量5%、ビニル含量34%)
※3: 1,6-ビス(N,N’-ジイソブチルチオカルバモイルジチオ)-ヘキサン
※4: N,N’-(4,4’-ジフェニルメタン)ビスマレイミド
※5: ブタジエンゴム、BR01、JSR社製
Claims (5)
- 更生タイヤ用クッションゴムと、台タイヤと、1層以上のゴム層からなるプレキュアトレッドゴムとを具える更生タイヤにおいて、
前記更生タイヤ用クッションゴムが、ゴム成分100質量%中、天然ゴム及び/又は合成ポリイソプレンゴムを60~100質量%の量で含むとともに、前記ゴム成分100質量部に対し、HAF級以上の高補強性カーボンブラックを30~50質量部の量で含むゴム組成物から形成されてなり、
前記更生タイヤ用クッションゴムからなるゴム層(A)の100%モジュラス(AM)が、3.0MPa以上6.0MPa未満であり、かつ
前記台タイヤの最外層(B)及び前記プレキュアトレッドゴムの最内層(C)が、ゴム成分100質量%中、天然ゴム及び/又は合成イソプレンゴムを60~100質量%の量で含むゴム組成物から形成されてなることを特徴とする更生タイヤ。 - 前記更生タイヤ用クッションゴムからなるゴム層(A)の100%モジュラス(AM)、前記台タイヤの最外層(B)の100%モジュラス(BM)、及び前記プレキュアトレッドゴムの最内層(C)の100%モジュラス(CM)が、下記式(i)及び(ii);
(i)60%≦AM/BM≦140%
(ii)60%≦AM/CM≦140%
の関係を満たすことを特徴とする請求項1~3のいずれかに記載の更生タイヤ。 - プレキュア方式で加硫接着されてなる航空機用更生タイヤであることを特徴とする請求項1~4のいずれかに記載の更生タイヤ。
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JP7414879B2 (ja) | 2016-07-29 | 2024-01-16 | 株式会社ブリヂストン | ゴム組成物及びそれを用いた更生タイヤ及びその更生タイヤの製造方法 |
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EP2532536B1 (en) | 2015-11-04 |
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EP2532536A1 (en) | 2012-12-12 |
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